Browse
Submit Data
Databases
API
Help

Dataset Information

30 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Catalyst accessibility to chemical reductants in metal-organic frameworks.

ABSTRACT: A molecular H2-evolving catalyst, [Fe2(cbdt)(CO)6] ([FeFe], cbdt = 3-carboxybenzene-1,2-dithiolate), has been attached covalently to an amino-functionalized MIL-101(Cr) through an amide bond. Chemical reduction experiments reveal that the MOF channels can be clogged by ion pairs that are formed between the oxidized reductant and the reduced catalyst. This effect is lessened in MIL-101-NH-[FeFe] with lower [FeFe] loadings. On longer timescales, it is shown that large proportions of the [FeFe] catalysts within the MOF engage in photochemical hydrogen production and the amount of produced hydrogen is proportional to the catalyst loading.

SUBMITTER: Roy S

PROVIDER: S-EPMC5836565 | biostudies-literature | 2017 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Catalyst accessibility to chemical reductants in metal-organic frameworks.

Roy Souvik S Pascanu Vlad V Pullen Sonja S González Miera Greco G Martín-Matute Belén B Ott Sascha S

Chemical communications (Cambridge, England) 20170306 22

A molecular H2-evolving catalyst, [Fe2(cbdt)(CO)6] ([FeFe], cbdt = 3-carboxybenzene-1,2-dithiolate), has been attached covalently to an amino-functionalized MIL-101(Cr) through an amide bond. Chemical reduction experiments reveal that the MOF channels can be clogged by ion pairs that are formed between the oxidized reductant and the reduced catalyst. This effect is lessened in MIL-101-NH-[FeFe] with lower [FeFe] loadings. On longer timescales, it is shown that la ...[more]

PMID: 28261731

Similar Datasets

Electronic chemical potentials of porous metal-organic frameworks.

Project description:The binding energy of an electron in a material is a fundamental characteristic, which determines a wealth of important chemical and physical properties. For metal-organic frameworks this quantity is hitherto unknown. We present a general approach for determining the vacuum level of porous metal-organic frameworks and apply it to obtain the first ionization energy for six prototype materials including zeolitic, covalent, and ionic frameworks. This approach for valence band alignment can explain observations relating to the electrochemical, optical, and electrical properties of porous frameworks.

| S-EPMC3946036 | biostudies-literature

Capturing chemical intuition in synthesis of metal-organic frameworks.

Project description:We report a methodology using machine learning to capture chemical intuition from a set of (partially) failed attempts to synthesize a metal-organic framework. We define chemical intuition as the collection of unwritten guidelines used by synthetic chemists to find the right synthesis conditions. As (partially) failed experiments usually remain unreported, we have reconstructed a typical track of failed experiments in a successful search for finding the optimal synthesis conditions that yields HKUST-1 with the highest surface area reported to date. We illustrate the importance of quantifying this chemical intuition for the synthesis of novel materials.

| S-EPMC6358622 | biostudies-literature

Architectural Stabilization of a Gold(III) Catalyst in Metal-Organic Frameworks.

Project description:Unimolecular decomposition pathways are challenging to address in transition-metal catalysis and have previously not been suppressed via incorporation into a solid support. Two robust metal-organic frameworks (IRMOF-10 and bio-MOF-100) are used for the architectural stabilization of a structurally well-defined gold(III) catalyst. The inherent rigidity of these materials is utilized to preclude a unimolecular decomposition pathway - reductive elimination. Through this architectural stabilization strategy, decomposition of the incorporated gold(III) catalyst in the metal-organic frameworks is not observed; in contrast, the homogeneous analogue is prone to decomposition in solution. Stabilization of the catalyst in these metal-organic frameworks precludes leaching and enables recyclability, which is crucial for productive heterogeneous catalysis.

| S-EPMC7153757 | biostudies-literature

Metal-Organic Frameworks as Catalyst Supports: Influence of Lattice Disorder on Metal Nanoparticle Formation.

Project description:Because of their high tunability and surface area, metal-organic frameworks (MOFs) show great promise as supports for metal nanoparticles. Depending on the synthesis route, MOFs may contain defects. Here, we show that highly crystalline MIL-100(Fe) and disordered Basolite® F300, with identical iron 1,3,5-benzenetricarboxylate composition, exhibit very divergent properties when used as a support for Pd nanoparticle deposition. While MIL-100(Fe) shows a regular MTN-zeotype crystal structure with two types of cages, Basolite® F300 lacks long-range order beyond 8 Å and has a single-pore system. The medium-range configurational linker-node disorder in Basolite® F300 results in a reduced number of Lewis acid sites, yielding more hydrophobic surface properties compared to hydrophilic MIL-100(Fe). The hydrophilic/hydrophobic nature of MIL-100(Fe) and Basolite® F300 impacts the amount of Pd and particle size distribution of Pd nanoparticles deposited during colloidal synthesis and dry impregnation methods, respectively. It is suggested that polar (apolar) solvents/precursors attractively interact with hydrophilic (hydrophobic) MOF surfaces, allowing tools at hand to increase the level of control over, for example, the nanoparticle size distribution.

| S-EPMC6519236 | biostudies-literature

A Flower-like In2O3 Catalyst Derived via Metal-Organic Frameworks for Photocatalytic Applications.

Project description:The most pressing concerns in environmental remediation are the design and development of catalysts with benign, low-cost, and efficient photocatalytic activity. The present study effectively generated a flower-like indium oxide (In2O3-MF) catalyst employing a convenient MOF-based solvothermal self-assembly technique. The In2O3-MF photocatalyst exhibits a flower-like structure, according to morphology and structural analysis. The enhanced photocatalytic activity of the In2O3-MF catalyst for 4-nitrophenol (4-NP) and methylene blue (MB) is likely due to its unique 3D structure, which includes a large surface area (486.95 m2 g-1), a wide spectrum response, and the prevention of electron-hole recombination compared to In2O3-MR (indium oxide-micro rod) and In2O3-MD (indium oxide-micro disc). In the presence of NaBH4 and visible light, the catalytic performances of the In2O3-MF, In2O3-MR, and In2O3-MD catalysts for the reduction of 4-NP and MB degradation were investigated. Using In2O3-MF as a catalyst, we were able to achieve a 99.32 percent reduction of 4-NP in 20 min and 99.2 percent degradation of MB in 3 min. Interestingly, the conversion rates of catalytic 4-NP and MB were still larger than 95 and 96 percent after five consecutive cycles of catalytic tests, suggesting that the In2O3-MF catalyst has outstanding catalytic performance and a high reutilization rate.

| S-EPMC9028932 | biostudies-literature

Improving the Mechanical Stability of Metal-Organic Frameworks Using Chemical Caryatids.

Project description:Metal-organic frameworks (MOFs) have emerged as versatile materials for applications ranging from gas separation and storage, catalysis, and sensing. The attractive feature of MOFs is that, by changing the ligand and/or metal, they can be chemically tuned to perform optimally for a given application. In most, if not all, of these applications one also needs a material that has a sufficient mechanical stability, but our understanding of how changes in the chemical structure influence mechanical stability is limited. In this work, we rationalize how the mechanical properties of MOFs are related to framework bonding topology and ligand structure. We illustrate that the functional groups on the organic ligands can either enhance the mechanical stability through formation of a secondary network of nonbonded interactions or soften the material by destabilizing the bonded network of a MOF. In addition, we show that synergistic effect of the bonding network of the material and the secondary network is required to achieve optimal mechanical stability of a MOF. The developed molecular insights in this work can be used for systematic improvement of the mechanical stability of the materials by careful selection of the functional groups.

| S-EPMC6062841 | biostudies-literature

Retrofitting metal-organic frameworks.

Project description:The post-synthetic installation of linker molecules between open-metal sites (OMSs) and undercoordinated metal-nodes in a metal-organic framework (MOF) - retrofitting - has recently been discovered as a powerful tool to manipulate macroscopic properties such as the mechanical robustness and the thermal expansion behavior. So far, the choice of cross linkers (CLs) that are used in retrofitting experiments is based on qualitative considerations. Here, we present a low-cost computational framework that provides experimentalists with a tool for evaluating various CLs for retrofitting a given MOF system with OMSs. After applying our approach to the prototypical system CL@Cu3BTC2 (BTC?=?1,3,5-benzentricarboxylate) the methodology was expanded to NOTT-100 and NOTT-101 MOFs, identifying several promising CLs for future CL@NOTT-100 and CL@NOTT-101 retrofitting experiments. The developed model is easily adaptable to other MOFs with OMSs and is set-up to be used by experimentalists, providing a guideline for the synthesis of new retrofitted MOFs with modified physicochemical properties.

| S-EPMC6820732 | biostudies-literature

Distinguishing Metal-Organic Frameworks.

Project description:We consider two metal-organic frameworks as identical if they share the same bond network respecting the atom types. An algorithm is presented that decides whether two metal-organic frameworks are the same. It is based on distinguishing structures by comparing a set of descriptors that is obtained from the bond network. We demonstrate our algorithm by analyzing the CoRe MOF database of DFT optimized structures with DDEC partial atomic charges using the program package ToposPro.

| S-EPMC5843951 | biostudies-literature

The Influence of Chemical Modification on Linker Rotational Dynamics in Metal-Organic Frameworks.

Project description:The robust synthetic flexibility of metal-organic frameworks (MOFs) offers a promising class of tailorable materials, for which the ability to tune specific physicochemical properties is highly desired. This is achievable only through a thorough description of the consequences for chemical manipulations both in structure and dynamics. Magic angle spinning solid-state NMR spectroscopy offers many modalities in this pursuit, particularly for dynamic studies. Herein, we employ a separated-local-field NMR approach to show how specific intraframework chemical modifications to MOF UiO-66 heavily modulate the dynamic evolution of the organic ring moiety over several orders of magnitude.

| S-EPMC6289050 | biostudies-literature

Multiphoton harvesting metal-organic frameworks.

Project description:Multiphoton upconversion is a process where two or more photons are absorbed simultaneously to excite an electron to an excited state and, subsequently, the relaxation of electron gives rise to the emission of a photon with frequency greater than those of the absorbed photons. Materials possessing such property attracted attention due to applications in biological imaging, photodynamic therapy, three-dimensional optical data storage, frequency-upconverted lasing and optical power limiting. Here we report four-photon upconversion in metal-organic frameworks containing the ligand, trans, trans-9,10-bis(4-pyridylethenyl)anthracene. The ligand has a symmetrical acceptor-π-donor-π-acceptor structure and a singlet biradical electronic ground state, which boosted its multiphoton absorption cross-sections. We demonstrate that the upconversion efficiency can be enhanced by Förster resonance energy transfer within host-guest metal-organic frameworks consisting of encapsulated high quantum yielding guest molecules. Using these strategies, metal-organic framework materials, which can exhibit frequency-upconverted photoluminescence excited by simultaneous multiphoton absorption, can be rationally designed and synthesized.

| S-EPMC4918338 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data